Substituted naphthacene-5,12-diones and their use

ABSTRACT

Substituted naphthacenediones of the formula I    &lt;IMAGE&gt;  (I)  in which R1 to R8 are H and at least one of R1 to R8, for example R2 and R3 or R2 and R6, are, for example, C1-C20alkoxy, C1-C20alkenoxy, C1-C20-alkylsulfinyl, -CN, -CF3, -NO2, -Si(CH3)3 or -COO(C1-C12alkyl), are suitable, when incorporated into polymers having hydroxyalkyl groups, for currentless deposition of metals onto the polymer surface. They are in some cases suitable as photoinitiators.

This is a divisional of Ser. No. 356,830, filed May 24, 1989, now U.S.Pat. No. 5,112,977.

The present invention relates to substituted naphthacene-5,12-diones andtheir use as photoinitiators or sensitizers for the photopolymerizationof compounds having at least one polymerizable or dimerizableethylenically unsaturated double bond, or for currentless deposition ofmetal onto the surface of polymers containing hydroxyalkyl groups.

Only few substituted naphthacene-5,12-diones have been disclosed todate. They are useful intermediates for the preparation oftetrachalcogenated tetracenes. Such tetrachalcogenated tetracenes formelectrically conductive charge transfer complexes with electron donors.2- and 2,3-carboxylic acids and carboxylic acid derivatives ofnaphthacene-5,12-dione are described, for example, in U.S. Pat. No.4,617,151. 2,7- and 2,8-difluoronaphthacene-5,12-dione are mentioned inDE-OS 3,635,124.

1-Hydroxyl- and 1-amino-naphthacene-5,12-diones which are substituted inthe 4-position and optionally in the 3-position are described asflurescent disperse dyestuffs in Japanese Patent Publication 49-81440.In Annales die Quimica, Ser. C. 81(2), pages 133-138 (1982), F. F. y T.Torres describes the preparation of 2-hydroxy-, 2-methoxy-, 2-ethoxy-and 2-(2-hydroxyethoxy)naphthacene-5,12-dione. Naphthacene-5,12-dioneshaving methoxy groups in the 6-, 7-, 8- and 9-positions are described,for example, in D. C. C. Smith, J. Chem. Soc., page 673 (1962), J. F. W.McOmie et al., Synthesis, page 416 (1973), and J. Laduranty et al., Can.J. Chem., volume 58, page 1161 (1980). 7-Methyl-naphthacene-5,12-dioneis described by L. K. Bee et al. in J. Chem. Res. (M), page 4301 (1981).2-Isopropyl-naphthacene-5,12-dione is mentioned in CA 86, 189773u(1977).

The present invention relates to compounds of the formula I ##STR2##wherein a) R¹, R² R³ and R⁴ are H and R⁵ to R⁸ are each H and at leastone of the radicals R⁵ to R⁸, independently of one another, is asubstituent from the group comprising C₁ -C₂₀ alkyl-X--_(p), with theexception of methyl and methoxy, C₂ -C₁₈ alkenyl-X--_(p), C₂ -C₁₈alkynyl-X--_(p), C₃ -C₈ cycloalkyl-X--_(p), (C₁ -C₁₂ alkyl)-C₃ -C₈cycloalkyl-X--_(p), C₃ -C₈ -cycloalkyl-C_(r) H_(2r) -X--_(p), (C₁ -C₁₂alkyl)-C₃ -C₈ cycloalkyl-C_(r) H_(2r) -X--_(p), phenyl-X--_(p), (C₁ -C₁₂alkyl) phenyl-X--_(p), phenyl-C_(r) H_(2r) -X--_(p) and (C₁ -C₁₂alkyl)phenyl-C_(r) H_(2r) -X--_(p) which are unsubstituted orsubstituted by halogen, --CN, furfuryl, --NR⁹ R¹⁰, --OR⁹, --SR⁹ orCOOR⁹, r is 1 or 2, p is 0 or 1 and X is --O--, --SO-- or --SO₂ --, orR⁵ to R⁸ independently are a substituent from the group comprisinghalogen, --NO₂, --CF₃, --CN, --NR⁹ R¹⁰, --COOR⁹ --CONR⁹ R¹⁰, --COCl,--SH, --Si(C₁ -C₄ alkyl)₃ and --O--C_(m) H_(2m) --O--_(n) R¹¹, or ineach case two adjacent radicals from R⁵ to R⁸ together are --CO--O--CO--or --CO--NR⁹ --CO--, R⁹ and R¹⁰ independently of one another are H, C₁-C₁₂ alkyl, phenyl or --C_(m) H_(2m) --O--_(q) R¹¹, or R⁹ and R¹⁰together are tetramethylene, pentamethylene, 3-oxapentylene or --CH₂ CH₂NR⁹ CH₂ CH₂ --, R¹¹ is H or C₁ -C₁₂ -alkyl, m is a number from 2 to 4, nis a number from 2 to 20 and q is a number from 1 to 20, or

b) R¹ to R⁸ independently of one another are H or one of thesubstituents defined above, including methyl and methoxy, wherein R¹,R⁴, R⁵ and R⁸ are also substituents with X in the meaning of --S-- andat least one of R¹ to R⁴ and R⁵ to R⁸ is a substituent, with theexception of R² and R⁶ or R⁷ as --F, or

c) R⁵ to R⁸ are H, at least one of R¹, R², R³ and R⁴ is a substituentand R¹ and R⁴ independently of one another are H or a substituent fromthe group comprising --NO₂, --CF₃, --CN, --COOR⁹, --CONR⁹ R¹⁰ --COCl,--Si(C₁ -C₄ -alkyl)₃, --S--C_(m) H_(2m) --O--_(n) R¹¹ and --O--C_(m)H_(2m) --O--_(n) R¹¹, and C₁ -C₂₀ alkyl-X--, where X is --SO-- or --SO₂,which is unsubstituted or substituted as defined under a); C₂ -C₁₈alkenyl-X--_(p), C₂ -C₁₈ alkynyl-X--_(p), C₃ -C₈ cycloalkyl-X--_(p), (C₁-C₁₂ alkyl)C₃ -C₈ cycloalkyl-X--_(p), C₃ -C₈ cycloalkyl-C_(r) H_(2r)-X--_(p) and (C₁ -C₁₂ alkyl)-C₃ -C₈ cycloalkyl-C_(r) H_(2r) -X--_(p) ;phenyl-X--_(p) and (C₁ -C₁₂ alkyl)-phenyl-X--_(p), where X is --SO-- or--SO₂ --; phenyl-C_(r) H_(2r) -X--_(p) and (C₁ -C₁₂ alkyl)-phenyl-C_(r)H_(2r) -X--_(p) ; and C₁ -C₂₀ alkylthio which is substituted as definedabove under a), phenyloxy, (C₁ -C₁₂ alkyl)phenyloxy and C₁ -C₂₀ alkoxywhich is substituted by halogen, --CN, --NR⁹ R¹⁰, --SR⁹, --OR⁹ or COOR;wherein R¹ is not --COOH if R² R³ and R⁴ are H, and R² and R³independently of one another are H or a substituent from the groupcomprising C₅ -C₂₀ alkyl, C₃ -C₂₀ alkoxy and C₁ -C₂₀ alkyl-X--, where Xis --SO-- or --SO₂ --, which are unsubstituted or substituted as definedabove under a); and phenyl-X--, (C₁ -C₁₂ alkyl)phenyl-X--_(p), (C₁ -C₁₂alkyl)phenyl-C_(r) H_(2r) -X--_(p), phenyl-C_(r) H_(2r) -X--_(p), C₂-C₂₀ alkenyl-X--_(p), C₂ -C₂₀ alkynyl-X--_(p), C₃ -C₈cycloalkyl-X--_(p), (C₁ -C₁₂ alkyl)-C₃ -C₈ cycloalkyl-X--_(p), C₃ -C₈cycloalkyl-C_(r) H_(2r) -X--_(p) or (C₁ -C₁₂ alkyl)-C₃ -C₈cycloalkyl-C_(r) H_(2r) -X--_(p), where X is --O--, --SO-- or --SO₂ ; orone of R² and R₃ or R² and R³ are a substituent from the groupcomprising phenyl which is substituted as defined above under a); or oneof R² and R³ or R² and R³ are a substituent from the group comprising C₁-C₄ alkyl and C₁ -C₂ alkoxy, which are substituted by halogen, --CN,--NR⁹ R¹⁰, --OR⁹ --SR⁹ or --COOR⁹, with the exception of 2-hydroxyethyl;or one of R² and R³ or R² and R³ are a substituent from the groupcomprising SH, --NO₂, --CF₃, --CN, --NR⁹ R¹⁰, --Si(C₁ -C₄ alkyl)₃ and--O--C_(m) H_(2m) --O--_(n) R¹¹, or one of R² and R³ are halogen,--COOR⁹, --CONR⁹ R¹⁰ or COCl and the other of R² and R³ is a substituentas defined under a), or the other of R² and R³ is H, if at least one ofR¹ and R⁴ is one of the substituents defined above; or R² and R³together are --CO--O--CO-- or --CO--NR⁹ --CO-- and at least one of R¹and R⁴ are one of the substituents defined above, or R₂ and R³ togetherindependently of one another are C₁ -C₂ alkoxy, wherein R⁹, R¹⁰, R¹¹, X,m, n, p, q, r and s are as defined under a), unless characterizedotherwise, or

d) R₅ to R⁸ are H and R¹ is unsubstituted C₁ -C₂₀ alkylthio, C₁ -C₂₀alkoxy, phenyloxy, phenylthio, C₁ -C₁₂ alkylphenyloxy or C₁ -C₁₂alkylphenylthio, or phenylthio or C₁ -C₁₂ alkylphenylthio which issubstituted as defined under a).

In C₁ -C₂₀ alkyl-X--_(p) R¹ to R⁸ in the context of the precedingdefinitions, the alkyl group can be linear or branched and canpreferably contain 1 to 18, in particular 1 to 12 and especially 1 to 6C atoms. Examples of alkyl groups are methyl, ethyl and the isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl and eicosyl. p is preferably 1.

In C₂ -C₁₈ alkenyl-X--_(p) R¹ to R⁸ in the context of the precedingdefinitions, the alkenyl group can be linear or branched and canpreferably contain 3 to 12, in particular 3 to 6, C atoms. The alkenylpreferably contains terminal double bonds. Some examples are ethenyl,allyl, prop-1-en-1- or -2-yl, but-1-en-1- or -2- or -3- or -4-yl,but-2-en-1- or -2-yl, pent-1-en- or pent-2-en-1- or -2- or -3- or -4- or-5-yl, hex-1-en- or hex-2-en- or hex-3-en-1- or -3- or -4- or -5-or-6-yl, heptenyl, octenyl, nonenyl, decenyl, undecyl, dodecenyl,tetracenyl, hexadecenyl and octadecenyl. p is preferably 1.

In C₂ -C₁₈ alkynyl-X--_(p) R¹ to R⁸ in the context of the precedingdefinitions, the alkynyl group can be linear or branched and canpreferably contain 3 to 12, in particular 3 to 6, C atoms. The triplebond is preferably in the terminal position. Some examples are ethynyl,propargyl, but-1-in-3- or -4-yl, but-2-in-1-yl, pent-1-in-3- or -4- or-5-yl, hex-1-in-3- or -4- or -5- or -6-yl, hex-2-in-1- or -4- or -5- or-6-yl, hex-3-in-1- or -2-yl, heptynyl, octynyl, nonynyl, decynyl,undecynyl and dodecyny, p is preferably 1.

C₃ -C₈ cycloalkyl-X--_(p) R¹ to R⁸ in the context of the precedingdefinitions can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl or cyclooctyl. X is preferably --O--. C₃ -C₆ cycloalkyl ispreferred. p is preferably 1.

In C₃ -C₈ cycloalkyl-C_(r) H_(2r) -X--_(p), (C₁ -C₁₂ alkyl)-C₃ -C₈cycloalkyl-X--_(p) or (C₁ -C₁₂ alkyl)-C₃ -C₈ -cycloalkyl-C_(r) H_(2r)-X--_(p) R¹ to R⁸ in the context of the preceding definitions, the alkylgroup can be linear or branched and can preferably contain 1 to 6, inparticular 1 to 4, C atoms. r in the --C₄ H_(2r) -- group ispreferably 1. X is preferably --O--. In these substituents, thecycloalkyl group is preferably C₃ -C₆ cycloalkyl. p is preferably 1.

In (C₁ -C₁₂ alkyl)phenyl-X--_(p), phenyl-C_(r) H_(2r) --X--_(p) or (C₁-C₁₂ alkyl)phenyl-X--_(p) R¹ to R⁸ in the context of the precedingdefinitions, the alkyl group can be linear or branched and canpreferably contain 1 to 6, in particular 1 to 4, C atoms. r in the--C_(r) H_(2r) -- group is preferably 1. p is preferably 1.

In the context of the preceding definitions, R¹ to R⁸ can beunsubstituted or substituted by one or more, preferably one to three andin particular one or two substituents. If the substituent is halogen,this is preferably --F, --Cl or --Br. If the substituent is --NR⁹ R¹⁰,R⁹ and R¹⁰ preferably independently of one another are H or C₁ -C₄alkyl, and in particular methyl or ethyl. If the substituent is --OR⁹,--SR⁹ or --COOR⁹, R⁹ is preferably H, C₁ -C₄ alkyl or --O--C_(m) H_(2m)O--_(n) R¹¹, in which R¹¹ is H or C₁ -C₄ alkyl, m is 2 or 3 and n is 1to 12.

Halogen R¹ to R⁸ in the context of the preceding definitions is, inparticular, --F, --Cl or --Br.

In --NR⁹ R¹⁰ or --CONR⁹ R¹⁰ R¹ to R⁸ in the context of the precedingdefinitions, R⁹ and R¹⁰ independently of one another are preferably C₁-C₆ alkyl, or R⁹ and R¹⁰ together are preferably tetra- orpentamethylene or 3-oxapentylene.

--Si(C₁ -C₄ alkyl)₃ R¹ to R⁸ in the context of the preceding definitionsis preferably --Si(C₁ or C₂ alkyl)₃, and in particular trimethylsilyl.

In --O--C_(m) H_(2m) --O--_(n) R¹¹ R¹ to R⁸ in the context of thepreceding definitions, R¹¹ is preferably H or C₁ -C₄ alkyl, m ispreferably 2 or 3 and n is preferably 1 to 12, in particular 1 to 6.

Adjacent radicals for the groups --CO--O--CO-- and --CO--NR⁹ --CO-- are,in particular, R² and R³ and/or R⁶ and R⁷.

Alkyl R⁹ and R¹⁰ preferably contain 1 to 6, in particular 1 to 4, Catoms and are, in particular, methyl or ethyl. The alkyl can be linearor branched.

In the group --C_(m) H_(2m) --O--_(n) R¹¹ R⁹ and R¹⁰, m is preferably 2or 3, n is 1 to 12, in particular 2 to 6, and R¹¹ is H or C₁ -C₄ alkyl.

In a preferred embodiment, R⁹ and R¹⁰ independently of one another areH, C₁ -C₄ alkyl or phenyl, or R⁹ and R¹⁰ together are tetramethylene,pentamethylene or 3-oxapentylene.

Preferred embodiments of compounds of the formula I are those in whicha) R⁵ or R⁸, or R⁴, R⁵ or R⁸, or R¹, R⁴, R⁵ or R⁸ are H, or b) R² or R³or R² and R³ are a substituent, or c) R¹, R² and R³ or R¹ and R² or R¹and R³ are a substituent, or d) R² and R³ or R² or R³ are a substituentand R⁶ or R⁷ or R⁶ and R⁷ are a substituent, or e) R¹, R² and R³ or R¹and R² or R¹ and R³ are a substituent and R⁴, R⁵ and R⁸ are H and R⁶ orR⁷ or R⁶ and R⁷ are H or a substituent. Preferred compounds of theformula I are those in which R⁴ is H, or in which p in the substituentis 1.

A preferred sub-group of compounds of the formula I comprises those inwhich R¹ to R⁴ and R⁵ and R⁸ are H; at least one of the radicals R⁶ orR⁷ is a substituent from the group comprising C₁ -C₁₈ alkyl-X--_(p),phenyl-X--_(p), (C₁ -C₆ alkyl)-phenyl-X--_(p), benzyl-X--_(p) and (C₁-C₆ alkyl)benzyl-X--_(p), which are unsubstituted or substituted by F,Cl, Br, --CN, --NR⁹ R¹⁰, --OR⁹, --SR⁹ or --COOR⁹ ; unsubstituted C₃ -C₁₂alkenoxy and C₃ -C₆ alkynoxy, the alkene or alkine group of which is notbonded to the O atom; and --F, --Cl, --Br, --NO₂, --CF₃, --CN, --NR⁹R¹⁰, COOR⁹, --CONR⁹ R¹⁰, --Si(CH₃)₃ and --O--C₂ H₄ O--_(n) R¹¹ ; R¹¹ isH or C₁ -C₄ alkyl; X is --O--, --SO-- or --SO₂ --, Y is --O--, p is 0 or1 and n is 2 to 20, and in which R⁹ and R¹⁰ are each H or C₁ -C₆ alkyl,or R⁹ and R¹⁰ together are tetra- or pentamethylene, 3-oxapentylene or--CH₂ CH₂ N-- (C₁ -C₆ alkyl)CH₂ CH₂.

Another preferred sub-group of compounds of the formula I comprisesthose in which R⁴, R⁵ and R⁸ are H; at least one of the radicals R¹, R²and R³ and at least one of the radicals R⁶ and R⁷ are a substituent fromthe group comprising C₁ -C₁₈ alkyl-X--_(p), including methyl andmethoxy, phenyl-X--_(p), (C₁ -C₆ alkyl)phenyl-X--_(p), benzyl-X--_(p)and (C₁ -C₆ alkyl)benzyl-X--_(p), which are unsubstituted or substitutedby F, Cl, Br, --CN, ONR⁹ R¹⁰, --OR⁹, --SR⁹ or --COOR⁹ ; unsubstituted C₃-C₁₂ alkenoxy or C₃ -C₆ alkynoxy, the alkene or alkine group of which isnot bonded to the O atom; and --F, --Cl, --Br, --NO₂, --CF₃, --CN, --NR⁹R¹⁰, --COOR⁹, --CONR⁹ R¹⁰, --Si(CH₃)₃ and O--C₂ H₄ O--_(n) R¹¹ ; R¹¹ isH or C₁ -C₄ alkyl; X is --O--, --SO-- or --SO₂ --, Y is --O--, p is 0 or1 and n is 2 to 20; and R⁹ and R¹⁰ are each H or C₁ -C₆ alkyl, or R⁹ andR¹⁰ together are tetra- or pentamethylene, 3-oxapentylene or --CH₂ CH₂N(C₁ -C₆ alkyl)CH₂ CH₂ --.

A preferred sub-group of compounds of the formula I also comprises thosein which R⁵ to R⁸ are H; R¹ and R⁴ independently of one another are H ora substituent from the group comprising --NO₂, --CF₃, --CN, --COOR⁹,--CONR⁹ R¹⁰, --Si(CH₃)₃, --S--C₂ H₄ --O--_(n) R¹¹ and --O--C₂ H₄--O--_(n) R¹¹, in which R⁹ and R¹⁰ are each H or C₁ -C₆ alkyl, or R⁹ andR¹⁰ together are tetramethylene, pentamethylene or 3-oxapentylene; R²and R³ independently of one another are H or a substituent from thegroup comprising C₅ -C₁₈ alkyl, C₃ -C₁₈ alkoxy, C₁ -C₁₈ alkyl-X--, whereX is --SO-- or --SO₂ --, phenyl-X--, (C₁ -C₆ alkyl)phenyl-X--,benzyl-X--_(p) or (C₁ - C₆ alkyl)benzyl-X--_(p) where X is --O--, --SO--or --SO₂ -- and p is 0 or 1, which are unsubstituted or substituted by--F, --Cl, --Br, --CN, --NR⁹ R¹⁰, --OR⁹, --SR⁹ or COOR⁹, andunsubstituted C₃ -C₁₂ alkoxy and C₃ -C₁₂ alkynoxy, the alkane or alkinegroup of which is not bonded to the O atom; and C₁ -C₄ alkyl and C₁ -C₂alkoxy which are substituted by --F, --Cl, --Br, --CN, --NR⁹ R¹⁰, --SR⁹or --OR⁹ ; and --F, --Cl, --Br, --NO₂, --CF₃, --CN, --NR⁹ R¹⁰,--Si(CH₃)₃ and --OC₂ H₄ O--_(n) R¹¹, where R¹¹ is H or C₁ -C₄ alkyl; orone of R² and R³ is --F, --Cl, --COOR⁹ or --CONR⁹ R¹⁰ and the other ofR² and R³ is a substituent as defined for R⁶ in Claim 8, or the other ofR² and R³ is H, if R¹ is a substituent; or R² and R³ are --COOR⁹ or--CONR⁹ R¹⁰, or together are --CO--O--CO-- or --CO--NR⁹ --CO--, if R¹ isa substituent as defined above; or R² and R³ independently are methoxyor ethoxy; or R⁹ and R¹⁰ are each H or C₁ -C₆ alkyl, or R⁹ and R¹⁰together are tetramethylene, pentamethylene, 3-oxapentylene or --CH₂ CH₂N(C₁ -C₆ alkyl)CH₂ CH₂ --, and n is 2 to 12.

Another preferred sub-group comprises those compounds of the formula Iin which R⁵ to R⁸ are H and R¹ is unsubstituted C₁ -C₁₂ alkylthio, C₁-C₁₂ alkoxy, phenyloxy, (C₁ -C₆ alkyl)phenyloxy or (C₁ -C₆alkyl)phenylthio or phenylthio or (C₁ -C₆ alkyl)phenylthio which issubstituted by --F, --Cl, --OH, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio.

Substituted alkyl R² and R³ are, in particular, C₁ -C₆ -, in particularC₁ - or C₂ -alkyl, which is substituted by --CN or --COO(C₁ -C₁₂ alkyl),or benzyl.

A particularly preferred sub-group comprises those compounds of theformula I in which R¹ is H, --NO₂, --CF₃ or --COO(C₁ -C₄ alkyl); R⁴, R⁵and R⁸ are H; R³, R⁶ and R⁷ are H and R² is C₃ to C₁₈ alkoxy, C₃ -C₁₂hydroxyalkyl or C₃ -C₆ dihydroxyalkyl, C₃ -C₁₂ alkenoxy or C₃ -C₆alkynoxy, in which the --O-- atom is not bonded to the alkene or alkinegroup, or --O--CH₂ CH₂ --O--_(n) R¹¹ where n is 2 to 12 and R¹¹ is H orC₁ -C₆ alkyl; phenyloxy which is unsubstituted or substituted by --F,--Cl, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio; --NR⁹ R¹⁰, whereR⁹ and R¹⁰ are C₁ -C₆ alkyl, or together are pentamethylene or3-oxapentylene; C₁ -C₆ alkyl-SO--, C₁ -C₄ alkyl-SO₂ --, phenyl-SO-- orphenyl-SO₂ --; C₁ -C₄ alkyl or benzyl which is substituted by --CN or--COO(C₁ -C₆ alkyl) or --CN or --CF₃ ; R² and R³ independently of oneanother are C₁ -C₂ alkoxy or --(O--CH₂ CH₂)₂ OR¹¹, where R¹¹ is H or C₁-C₆ alkyl and n is 2 to 12; or --F, --Cl or --Br, or are as definedabove for R² ; and R⁵ and R⁸ are H, and R⁶ and R⁷ independently are H,--F, --Cl, --Br, --CN, --CF₃, --Si(CH₃)₃, --NO₂, C₁ -C₁₂ alkoxy or--COO(C₁ -C₆ alkyl), with the exception of R² and R⁶ or R⁷ as --F and R¹R⁴, R⁵ and R² as H; or R¹ to R⁵ and R⁸ are H, R⁶ or R⁷ is H and R⁷ or R⁶or R⁶ and R⁷ independently of one another are --F, --Cl, --Br, --CN,--NO₂, --CF₃, --Si(CH₃)₃, --NO₂, --COO(C₁ -C₄ alkyl) or C₁ -C₁₂ alkoxy.

The compounds of the formula I can be prepared by reacting, by aFriedel-Crafts reaction, a naphthalenedicarboxylic anhydride of theformula II ##STR3## with a benzene of the formula III ##STR4## in whichR¹ to R⁸ are as defined above, in the presence of a Lewis acid, and ifappropriate substituting compounds of the formula I in which at leastone of R¹ to R⁸ is --NO₂ or halogen with a nucleophilic compound.Halogen is preferably --Br, --Cl and, in particular, --F. Compoundswhich are suitable for the nucleophilic substitution are, in particular,those of the formula (R¹ to R⁸ --X--H, in which X is --O--, --S--,--SO-- or --SO₂, H--NR⁹ R¹⁰, malonic acid esters or nitriles andphenylacetonitrile. The compounds can be used in the form of theiralkali metal salts, for example Li, Na or K salts. It is also possiblefor the nucleophilic substitution to be carried out in the presence ofbases, for example alkali metal hydroxide solutions or alkali metalcarbonates.

The compounds of the formula I can also be prepared by reacting, in aDiols-Alder reaction, a compound of the formula IV ##STR5## in which R⁵,R⁶, R⁷ and R⁸ are as defined above and X¹ and X² independently of oneanother are --Cl, --Br or --I, with a compound of the formula V ##STR6##in which R¹, R², R³ and R⁴ are as defined above, HX¹ and HX² being splitoff. In the substituents R¹ to R⁸, p is preferably 1.

The reaction is advantageously carried out at temperatures of 50° to250° C., preferably 80° to 200° C. An inert solvent is advantageouslyused, for example polar aprotic solvents. Some examples are aromatichydrocarbons (benzene, toluene, xylene, chlorobenzene anddichlorobenzene), nitriles (acetonitrile) and ethers (dibutyl ether,dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and diethyleneglycol dimethyl ether). The products can be isolated and purified bycustomary methods, for example crystallization, sublimation orchromatography.

Compounds of the formula IV are known in some cases (see, for example,H. P. Cava et al., J. Am. Chem. Soc., page 1701 (1957) and J. W. Bartonet al., J. Chem. Soc. Perkin Trans. 1, pages 967-971 (1986)), or can beprepared by analogous processes. The substituted 1,2-bis(dichloro- ordiboromomethyl)benzenes required for the preparation are likewise knownin some cases or are obtainable by customary electrophilic ornucleophilic substitution reactions on corresponding o-dimethylbenzenesand subsequent chlorination or bromination of the products with, forexample, N-chloro- or N-bromosuccinimide.

The 1,4-naphthoquinones of the formula V are known and are obtainable,for example, by nucleophilic substitution of halogeno- ornitro-1,4-naphthoquinones, which may be protected and substituted, with,for example, the compounds described above in the presence of alkalimetal compounds, (K₂ CO₃, Cs₂ CO₃, KOH, NaOH, NaNH₂, NaOCH₃ or NaOC₂H₅), or with alkali metal compounds, for example of Li, K, Na, Rb, orCs. Halogeno-and nitro-naphthoquinones are described, for example, inHouben-Weyl, Chinone I, (Quinones I), volume 7/3 b (1977). Thenaphthoquinones of the formula V can also be prepared in a known mannerby electrophilic or nucleophilic substitution of unsubstituted orsubstituted naphthalenes or dihydro- or tetrahydronaphthalenes andsubsequent conversion into the substituted 1,4-naphthoquinones.

Compounds of the formula I can also be prepared by reacting1,2-bis(dihalogenomethyl)benzenes of the formula ##STR7## in which Y¹ isCl, Br or I, with a compound of the formula V in the presence of NaI inan organic solvent. This method is described by J. W. McOmie inSynthesis, pages 416-417 (1973).

Compounds of the formula I can also be obtained by reactinganthracene-1,4-quinones of the formula ##STR8## with an α-pyrone of theformula VI ##STR9## or a butadiene of the formula VII ##STR10## in whichR¹¹ is C₁ -C₆ alkyl and R⁹ is as defined above, and is preferably C₁ -C₆alkyl. This method and the preparation of α-pyrones is described in U.S.Pat. No. 4,617,151 and EP-A-0,195,743.

Compounds of the formulae VI and VII are obtainable, for example, asfollows: In these formulae, X³ is an alkali metal: ##STR11##

If R¹ to R⁸ are a polyoxaalkylene radical, such compounds are alsoobtained by reacting compounds of the formula I where R¹ to R⁸ arehydroxyalkyl with epoxides. It is furthermore possible to convert theradicals R¹ to R⁸ by classical reactions, for example hydrolysis,esterification or transesterification, amidation, oxidation orreduction. Carboxylic acid esters can be converted into thetrifluoromethyl derivatives with HF/SF₄ in a known manner.

The compounds of the formula I are in general crystalline and aredistinguished by a high heat stability. Compounds with oxy, sulfinyl oralkyl substituents can be dissolved very readily in curablecompositions, if appropriate together with a solvent.

By themselves or together with H donors, for example tertiary amines oralcohols or phenylacetic acid derivatives, they are suitable as activephotoinitiators or sensitizers for photo-induced polymerization ordimerization of ethylenically unsaturated compounds. In this applicationthey are distinguished by a good photosensitivity and activity over awavelength range from about 200 nm (UV light) to about 600 nm.

The properties of the compounds according to the invention, for examplesolubility, melting point and absorption range, can be influenced in acontrolled manner by the choice of substituents.

The present invention furthermore relates to a composition which can bepolymerized by radiation and contains (a) at least one non-volatile,monomeric, oligomeric or polymeric compound having at least onephotopolymerizable or photodimerizable ethylenically unsaturated doublebond and (b) at least one compound of the formula Ia as a photoinitiatoror sensitizer, ##STR12## in which at least one of R¹ to R⁴, R⁶ and R⁷ isa substituent, R¹ and R⁴ independently of one another are H, C₁ -C₁₈alkoxy or --O--C_(m) H_(2m) --O--_(n) R¹¹, where m is 2 to 4, n is 1 to20 and R¹¹ is H or C₁ -C₁₂ alkyl, R², R³, R⁶ and R⁷ independently of oneanother are H, C₁ -C₁₈ alkoxy, C₁ -C₁₈ alkyl--SO--, --O--C_(m) H_(2m)--O--_(n) R¹¹, --COO(C₁ -C₁₈ alkyl), --COO--C_(m) H_(2m) --O--_(n) R¹¹or C₁ -C₆ alkyl, benzyl or C₁ -C₆ alkoxy which is substituted by 1 or 2--COO(C₁ -C₁₈ alkyl) or --COO--C_(m) H_(2m) --O--_(n) R¹¹, wherein R¹¹,m and n are as defined above.

The compositions can contain further photoinitiators or sensitizersother than (b).

The amount of compounds according to the invention added essentiallydepends on economic aspects, on their solubilities and on the desiredsensitivity. In general, 0.01 to 20, preferably 0.05-10 and inparticular 0.1 to 5% by weight, based on component (a), is used.

Possible components (a) are those ethylenically unsaturated monomeric,oligomeric and polymeric compounds which react by photopolymerization togive higher molecular weight products and during this change theirsolubility.

Examples of particularly suitable compounds are esters of ethylenicallyunsaturated carboxylic acids and polyols or polyepoxides, and polymershaving ethylenically unsaturated groups in the chain or in side groups,for example unsaturated polyesters, polyamides and polyurethanes andcopolymers thereof, polybutadiene and butadiene copolymers, polyisopreneand isoprene copolymers, polymers and copolymers having (meth)acrylicgroups in side chains, and mixtures of one or more such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylicacid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fattyacids, such as linolenic acid or oleic acid. Acrylic and methacrylicacid are preferred.

Aromatic and in particular aliphatic and cycloaliphatic polyols aresuitable as the polyols. Examples of aromatic polyols are hydroquinone,4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxphenyl)-propane and novolaks andcresols. Examples of polyepoxides are those based on the polyolsmentioned, in particular the aromatic polyols and epichlorohydrin.Polymers or copolymers containing hydroxyl groups in the polymer chainor in side groups, for example polyvinyl alcohol and copolymers thereofor polymethacrylic acid hydroxyalkyl esters or copolymers thereof, arefurthermore also suitable as polyols. Other suitable polyols areoligoesters containing hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols are alkylenediolshaving preferably 2 to 12 C atoms, such as ethylene glycol, 1,2- or1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol,octanediol, dodecanediol, diethylene glycol, triethylene glycol,polyethylene glycols having molecular weights of preferably 200 to 1500,1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,1,4-dihydroxymethylcyclohexane, glycerol, tris-(β-hydroxyethyl)amine,trimethylolethane, trimethylolpropane, pentaerythritol,dipentaerythritol and sorbitol.

The polyols can be partly or completely esterified with one or differentunsaturated carboxylic acids, it being possible for the free hydroxylgroups in partial esters to be modified, for example etherified oresterified with other carboxylic acids.

Examples of esters are: trimethylolpropane triacrylate,trimethylolethane triacrylate, trimethylolpropane trimethacrylate,trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate,triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritoltetraacrylate, dipentaerythritol diacrylate, dipentaerythritoltriacrylate, dipentaerythritol tetraacrylate, dipentaerythritolpentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritoloctaacrylate, pentaerythritol dimethacrylate, pentaerythritoltrimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritoltrimethacrylate, tripentaerythritol octamethacrylate, pentaerrythritoldiitaconate, dipentaerythritol triitaconate, dipentaerythritolpentaitaconate, dipentaerythritol hexaitaconate, ethylene glycoldimethacrylate, 1,3-butanediol diacrylate, 1,3-butanedioldimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate,sorbitol tetraacrylate, modified pentaerythritol triacrylate, sorbitoltetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,oligoester acrylates and methacrylates, glycerol di- and triacrylate,1,4-cyclohexane diacrylate, bisacrylates and bismethacrylates ofpolyethylene glycol having a molecular weight of 200-1500, or mixturesthereof.

The amides of identical or different unsaturated carboxylic acids witharomatic, cycloaliphatic and aliphatic polyamines having preferably 2 to6, in particular 2 to 4, amino groups are also suitable as component(a). Examples of such polyamines are ethylenediamine, 1,2- or1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine,1,5-pentylenediamine,

1,6-hexylenediamine, octylenediamine, dodecylenediamine,1,4-diaminocyclohexane, isophoronediamine, phenylenediamine,bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine,triethylenetetramine and di-(β-aminoethoxy)- ordi(β-aminopropoxy)ethane. Other suitable polyamines are polymers andcopolymers having amino groups in the side chain and oligoamides havingamino end groups.

Examples of such unsaturated amides are: methylene-bis-acrylamide,1,6-hexamethylene-bis-acrylamide,diethylenetriamine-tris-methacrylamide,bis(methacrylamidopropoxy)-ethane, β-methacrylamidoethyl methacrylate,N[(β-hydroxyethoxy)ethyl]-acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example,from maleic acid and diols or diamines. Some of the maleic acid can bereplaced by other dicarboxylic acids. They can be used together withethylenically unsaturated comonomers, for example styrene. Thepolyesters and polyamides can also be derived from dicarboxylic acidsand ethylenically unsaturated diols or diamines, in particular fromlonger-chain compounds having, for example, 6 to 20 C atoms. Examples ofpolyurethanes are those which are built up from saturated or unsaturateddiisocyanates and unsaturated or saturated diols.

Polybutadiene and polyisoprene and copolymers thereof are known.Examples of suitable comonomers are polyolefins, such as ethylene,propene, butene and hexene, (meth)acrylates, acrylonitrile, styrene orvinyl chloride. Polymers having (meth)acrylate groups in the side chainare likewise known. They can be, for example, reaction products ofnovolak-based epoxy resins with (meth)acrylic acid, homo- or copolymersof polyvinyl alcohol or hydroxyalkyl derivatives thereof esterified with(meth)acrylic acid, or homo- and copolymers of (meth)acrylatesesterified with hydroxyalkyl (meth)acrylates.

The photopolymerizable compounds are employed by themselves or in anydesired mixtures. Mixtures of polyol (meth)acrylates are preferablyused.

Suitable dimerizable compounds are those which contain, for example,cinnamic acid radicals, dimethylmaleimidyl radicals ##STR13## radicals.These radicals are in general bonded to oligomers or polymers, forexample in the polymer chain or as side groups. Polymers havingdimethylmaleimidyl groups are described, for example, in DE-A-2,626,795.Epoxy resins containing ##STR14## groups are described, for example, inDE-A-2,342,407.

Binders can also be added to the compositions according to theinvention, and this is particularly advantageous if photopolymerizableor photodimerizable compounds are liquid or viscous substances. Theamount of binder can be, for example, 5-95, preferably 10-90 and inparticular 50-90% by weight, based on the entire composition. The binderis chosen according to the field of use and the properties required forthis, such as developability in aqueous and organic solvent systems,adhesion to substrates and oxygen sensitivity.

Examples of suitable binders are polymers having a molecular weight ofabout 5000-2000000, preferably 10000 to 1000000. Examples are: homo- andcopolymeric acrylates and methacrylates, for example copolymers ofmethyl methacrylate/ethyl acrylate/methacrylic acid, poly(methacrylicacid alkyl esters) and poly(acrylic acid alkyl esters); cellulose estersand ethers, such as cellulose acetate, cellulose acetobutyrate,methylcellulose and ethylcellulose; polyvinylbutyral, polyvinylformal,cyclized rubber and polyethers, such as polyethylene oxide,polypropylene oxide and polytetrahydrofuran; and polystyrene,polycarbonate, polyurethane, chlorinated polyolefins, polyvinylchloride, copolymers of vinyl chloride/vinylidine chloride, copolymersof vinylidine chloride with acrylonitrile, methyl methacrylate and vinylacetate, polyvinyl acetate, copoly(ethylene/vinyl acetate), polyamides,such as polycaprolactam and poly(hexamethyleneadipamide), andpolyesters, such as poly(ethylene glycol terephthalate) andpoly(hexamethylene glycol succinate).

The compositions according to the invention are suitable as coatingagents for all types of substrates, for example wood, paper, ceramics,plastics, such as polyester and cellulose acetate films, and metals,such as copper and aluminum, onto which a protective layer or aphotographic image is to be applied by photopolymerization. The presentinvention also relates to the coated substrates and a process forapplication of photographic images to the substrates. The coatedsubstrates can also be used as recording material for holograms (volumephase diagram), it being advantageous that no wet development isnecessary for this purpose.

The substrates can be coated by applying a liquid composition or asolution or suspension to the substrate. Liquid compositions withoutsolvents are preferred.

The choice of solvent and the concentration depends chiefly on thenature of the composition and on the coating process. The composition isapplied uniformly to a substrate by means of known coating processes,for example by dipping, knife-coating, curtain coating processes,electrophoresis, brushing on, spraying or reverse roll coating. Theamount applied (coating thickness) and nature of the substrate (coatingcarrier) depend on the desired field of application. Examples of coatingcarriers which are used for photographic recording of information arefilms of polyester, cellulose acetate or paper coated with plastic;specially treated aluminum for offset printing plates and laminatescoated with copper for the production of printed circuits. The coatingthicknesses for photographic materials and offset printing plates are ingeneral about 0.5 to about 10 μm; for printed circuits, they are ingeneral 1 to about 100 μm. If solvents are also used, these are removedafter the coating process.

Photocurable compositions such as are used for the various purposesusually contain a number of other additives in addition to thephotopolymerizable compounds and the photoinitiators. It is thus oftenusual to add thermal inhibitors which above all are intended forprotection from premature polymerization during preparation of thecompositions by mixing of the components. Hydroquinone, hydroquinonederivatives, p-methoxyphenyl, β-naphthols or sterically hinderedphenols, such as, for example, 2,6-di(tert-butyl)-p-cresol, for example,are used for this. Small amounts of UV absorbers, for example those ofthe benztriazole, benzophenone or oxalanilide type, can furthermore beadded. Light stabilizers of the sterically hindered amine type (HALS)can likewise be added.

Copper compounds, such as copper naphthenate, stearate or octoate,phosphorus compounds, such as triphenylphosphine, tributylphosphine,triethyl phosphite, triphenyl phosphite or tribenzyl phosphite,quaternary ammonium compounds, such as tetramethylammonium chloride ortrimethylbenzylammonium chloride, or hydroxylamine derivatives, forexample N-diethylhydroxylamine, can be added to increase the stabilityon storage in the dark.

In order to exclude the inhibiting action of atmospheric oxygen,paraffin or similar waxy substances are frequently added to photocurablemixtures. At the start of the polymerization, these float out because ofa lack of solubility in the polymer and form a transparent surface layerwhich prevents access by air.

Other customary additives are photosensitizers which absorb in certainwavelengths and release the absorbed energy to the initiators orthemselves function as an additional initiator. Examples of these are,in particular, thioxanthone, anthracene, anthraquinone and coumarinderivatives.

Other customary additives are accelerators of the amine type, which areof particular importance in pigmented formulations, since they act aschain transfer agents. Examples of these are N-methyldiethanolamine,triethylamine, ethyl p-dimethylaminobenzoate or Michler's ketone. Theaction of the amines can be intensified by addition of aromatic ketonesof the benzophenone type.

Examples of other customary additives are fillers, pigments, dyes,adhesives, wetting agents and flow control agents.

Photocuring is of great importance for printing inks, since the dryingtime of the binder is a decisive factor for the rate of production ofgraphics products and should be of the order of fractions of seconds.UV-curable printing inks are of particular importance for screenprinting.

The photocurable compositions according to the invention are alsosuitable for the production of printing plates, in particularflexographic printing plates. Mixtures of soluble linear polyamides orof styrenebutadiene rubber with photopolymerizable monomers, for exampleacrylamides or acrylates, and a photoinitiator are used, for example,for this. Films and plates of these systems are exposed via the negative(or positive) of the print master and the non-cured portions are theneluted with a solvent.

Another field of use of photocuring is coating of metals, for example inthe varnishing of sheet metals for tubes, cans or bottle closures, andphotocuring of coatings of plastic, for example of PVC-based floor orwall coverings.

Examples of the photocuring of coatings on paper are colourlessvarnishing of labels, gramophone record covers or book covers.

The use of the photocurable compositions for imaging processes and foroptical production of information carriers is also important. In thisinstance, the layer applied to the carrier (wet or dry) is irradiatedwith short-wave light through a photomask and the non-exposed areas ofthe coating are removed by treatment with a solvent (=developer). Theexposed areas are crosslinked polymer and therefore insoluble and remainon the carrier. Visible images are formed after appropriate staining. Ifthe carrier is a metalized layer, after exposure and development themetal can be etched away at the non-exposed areas or reinforced byelectroplating. Printed circuits can be produced in this manner. Thecomposition according to the invention can also be used as aphotoresist.

Suitable light sources for the exposure to light are those with a highcontent of short-wave light. Appropriate industrial devices and varioustypes of lamps are available today for this purpose. Examples are carbonarc lamps, xenon arc lamps, mercury vapour lamps, metal-halogen lamps,fluorescent lamps, argon lamps or photographic floodlamps. Laser lightsources have also recently been used. These have the advantage that nophotomasks are needed; the controlled laser beam writes directly on thephotocurable layer.

The invention thus also relates to a) a coated substrate which is coatedon at least one surface with a composition according to the invention;b) a process for the photographic production of relief images orcoatings, which comprises exposing a coated substrate imagewise or overareas and subsequently removing non-exposed portions with a solvent; c)the use of compounds of the formula Ia as initiators and sensitizers forphotopolymerization or photodimerization of non-volatile monomeric,oligomeric or polymeric compounds having at least one photopolymerizableor photodimerizable ethylenically unsaturated double bond; and d) theuse of a composition according to the invention for the preparation ofvarnishes, printing inks, printing plates and resist materials and as animage-recording material and coating agent.

The compounds of the formula I are also useful intermediates for thepreparation of substituted tetrathio- and tetraselenotetracenes (cf.U.S. Pat. No. 4,617,151). Electrically conductive charge transfercomplexes (CT complexes) can be prepared from such chalcogenatedtetracenes with electron acceptors. With the functional substituentsthereof, they can be bonded to polymers, for example incorporated intopolymers as side groups (cf. U.S. Pat. No. 4,617,151). The CT complexesare also suitable for the production of, for example, antistaticcoatings of photographic film elements, magnetic tapes,electrophotographic film elements and electronic components (see U.S.Pat. No. 3,634,336). The chalcogenated tetracenes furthermore haveelectrochromic properties; they can be used for electrochromic displays.They are also suitable as laser-optical data stores [Nach. Chem. Techn.Lab. 35, page 255 et seq. (1987)] and as the anode material in organicsolid state batteries (EP-A-0,090,598). CT complexes of substitutedtetrathio- or tetraselenotetracenes can also be incorporated intothermoplastic, thermosetting or elastomeric polymers to achieveantistatic properties. For this, for example, the substituted tetrathio-or tetraselenotetracenes are advantageously dissolved together with asoluble polymer or a precursor thereof, and an electron acceptor, forexample a halogen-forming agent (organic halogenated compounds, forexample bromoform, trichlorobromomethane, tetrabromomethane,hexachloropropane, perchlorobutadiene, 1,3- or 1,4-dichloro-2-butene,1,4-bis(trichloromethyl)-benzene, iodoacetonitrile, iodoform,tetrachloroethylene, perchlorocyclobutadiene and N-chloro-, -bromo- or-iodosuccinimide), if appropriate together with another inert solvent,and the excess halogen-forming agent and the solvent are evaporated offat elevated temperature. The composition formed contains a network ofneedle-shaped crystals of the CT complex in the polymer if thechalcogenated tetracene is unsubstituted or contains small substituents(for example F, CH3 or CF3). Such compositions have a high electricalconductivity. This can be improved further if a substituted tetrathio-or tetraselenotetracene prepared from the compounds of the formula Iwhich forms no such network and is present in the polymer matrix in finedistribution is also used, since such substituted tetrathio- ortetraselenotetracenes have only a low tendency, if any, to crystallizein the polymer. Naphthacene-5,12-diones can furthermore also be used inelectrochromic display elements (JP-OS 61-43680).

The compounds of the formula I can also be used for currentlessdeposition of metals onto the surface of polymers containinghydroxyalkyl groups, for example copolymers of methacrylates with alkyland hydroxyalkyl ester groups, or epoxy resins which are cured, forexample, with amino alcohols. For this, compounds of the formula I aremixed with the polymers, for example in an amount of 0.1 to 10% byweight, based on the polymer, and the mixture is exposed, if appropriateunder a negative master, and treated with a metallizing bath whichpreferably contains a copper salt.

The following examples illustrate the invention in more detail.

A) PREPARATION EXAMPLES EXAMPLES 1-17

2-n-Octyloxy-naphthacene-5,12-dione

20 g (72.4 mmol) of 2-fluoro-naphthacene-5,12-dione, 94.3 g of1-octanol, 30.01 g (217.2 mmol) of anhydrous potassium carbonate and 200ml of dimethyl sulfoxide (DMSO) are stirred at a bath temperature of100° C. for 20 hours. The reaction mixture is cooled, toluene/dilutehydrochloric acid are added and the organic phase is separated off,washed twice with water, dried with sodium sulfate and evaporated. Theresidue is washed with pentane and recrystallized from cyclohexane.Yield: 22.9 g (82%), melting point 127°-129° C.

The compounds described in Table 1 are prepared analogously, using thecorresponding alcohols.

                                      TABLE 1                                     __________________________________________________________________________     ##STR15##                                                                                              Reaction                                            Example                                                                            R                    time (hours)                                                                         Bath temp. (°C.)                                                                Yield (%)                                                                           melting point                 __________________________________________________________________________                                                    (°C.)                        ##STR16##           15     130      41    85-90                         3    (CH.sub.2).sub.2CH(CH.sub.3)(CH.sub.2).sub.3CH(CH.sub.3).sub.2                                     16     140      12    102-104                       4    CH.sub.2CCH          23      60      84    160-163                       5    H*.sup.)             18     130      61    >250                          6    CH.sub.3             21      60      94    237- 239                      7    CH.sub.2CH.sub.3      5     100      95    198-200                       8    CH(CH.sub.3).sub.2   18     127      34    112-114                       9                                                                                   ##STR17##           18     110      46    200-203                       10                                                                            n-C.sub.18 H.sub.37                                                                26                   120    79        58-103                             11                                                                                  ##STR18##            1     100      86    217-219                       12                                                                                  ##STR19##           1/4    100      83    222-223                       13                                                                                  ##STR20##           1/3    105      84    203-205                       14   (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                                                                 3     100      82    130-132                       15   CH.sub.2CH(OH)CH.sub.2OH                                                                            3     100      76    187-191                       16   (CH.sub.2CH.sub.2O)CH.sub.3                                                                         8     100      72    90-93                         17   (CH.sub.2CH.sub.2O).sub.12CH.sub.3                                                                  8     100      60    (partly                       __________________________________________________________________________                                                    crystalline)                   *)Introduction of H.sub.2 S                                              

Examples 18-23

2-(2'-Hydroxyethoxy)-naphthacene-5,12-dione 27.6 g (0.1 mol) of2-fluoro-5,12-naphthacenequinone, 32.5 g (0.1 mol) of Cs₂ CO₃ and 300 mlof ethylene glycol are introduced into a sulfonating flask undernitrogen. After heating to 125° C., the mixture is stirred for 3 h. Thereaction mixture is then poured into 3000 ml of water containinghydrochloric acid and the product which has precipitated is filtered offand washed several times with water. After drying in vacuo at 80° C.,30.3 g (97.1%) of pure product are obtained, melting point 208.8° C. Theprocedure is analogous in Examples 19-23 (see Table 2).

Examples 24-27

2-(3-Butenoxy)-naphthacene-5,12-dione 10 g (0.036 mol) of2-fluoro-5,12-naphthacenequinone, 26 g (0.028 mol) of Cs₂ CO₃ and 10.41g (0.14 mol) of 3-butanol are introduced into 200 ml of DMF undernitrogen. The reaction mixture is heated to 125° C. and stirred for 41/2h. After precipitation in 4000 ml of water containing hydrochloric acid,the product is filtered off (crude yield 94%). Chromatography on silicagel (CH₂ Cl₂) gives 63% pure product; melting point 149° C. Theprocedure in Examples 25-27 is analogous (see Table 2).

                                      TABLE 2                                     __________________________________________________________________________     ##STR21##                                                                    Example                                                                            R              m.p. (°C.)                                                                  Reaction time (hours)                                                                    Yield (%)                                                                           Solvent                                                                            Reaction temp.                 __________________________________________________________________________                                                   (°C.)                   18   O(CH.sub.2).sub.2OH                                                                          208  31/4       97    i.S. 125                            19   O(CH.sub.2).sub.4OH                                                                          190  71/2       70    i.S. 120                            20   O(CH.sub.2).sub.6OH                                                                          153  11/4       70    DMSO 120                            21   O(CH.sub.2).sub.10OH                                                                         113   3/4       73    i.S. 125                            22   OCH.sub.2(CF.sub.2).sub.3CH.sub.2OH                                                          167  31/4       79    DMF   90                            23                                                                                  ##STR22##     144-147                                                                            191/2      75    DMF  110                            24   OCH.sub. 2CHCH.sub.2                                                                         164  51/4       91    i.S.  95                            25   O(CH.sub.2).sub.2CHCH.sub.2                                                                  152  41/2       84    DMF  130                            26   O(CH.sub.2).sub.4CHCH.sub.2                                                                  125  51/2       78    DMF  130                            27   O(CH.sub.2).sub.9CHCH.sub.2                                                                   98  51/2       65    i.S. 130                            __________________________________________________________________________     i.S.: alcohol is identical to the solvent                                     DMF: dimethylformamide                                                   

Examples 28-32

2-(N-Piperidinyl)-naphthacene-5,12-dione

1 g (3.62 mmol) of 2-fluoro-naphthacene-5,12-dione, 0.92 g (10.86 mmol)of piperidine, 1.50 g (10.86 mmol) of potassium carbonate and 10 ml ofDMSO are stirred at a bath temperature of 60° C. for 45 minutes. Aftercooling, the mixture is poured onto water and the orange product isfiltered off. The crystals are dissolved in tetrahydrofuran(THF)/toluene and the solution is dried over sodium sulfate andevaporated. The residue is recrystallized from toluene/pentane. Yield:1.11 g (90%); melting point 230°-233° C.

The procedure in Examples 29-32 is analogous (see Table 3).

                  TABLE 3                                                         ______________________________________                                         ##STR23##                                                                                        Re-                                                                           action  Bath                                              Ex-                 time    temp. Yield m.p.                                  ample R             (hours) (°C.)                                                                        (%)   (°C.)                          ______________________________________                                        29    N(Et).sub.2.sup.1)                                                                          25      50    84    170-175                               30    N(Bu).sub.2.sup.2)                                                                          24      60    69    167-170                               31                                                                                   ##STR24##    1/2     60    71    245-250                               32                                                                                   ##STR25##     7      60    88    230-235                               ______________________________________                                         .sup.1) ethyl                                                                 .sup.2) butyl                                                            

Example 33

2-(Phenylsulfonyl-)-naphthacene-5,12-dione

1 g (3.62 mmol) of 2-fluoro-naphthacene-5,12-dione, 0.89 g (5.43 mmol)of benzenesulfinic acid sodium salt (sodium benzenesulfinate) and 10 mlof DMSO are stirred at 100° C, for 3 hours. After cooling, the mixtureis poured onto water. The crystals are filtered off and dissolved inTHF/toluene. The solution is dried over sodium sulfate and evaporated.The residue is recrystallized from THF/toluene/pentane. Yield: 1.35 g(94%), melting point >260° C.

Example 34

2-(Methylsulfonyl-)naphthacene-5,12-dione2-(Methylsulfonyl-)napthacene-5,12-dione is prepared analogously toExample 33 using sodium methanesulfonate and by stirring at 80° C. forsix hours. Yield: 57%.

Example 35

Methyl-(2-naphthacene-5,12-dionyl) sulfoxide

a) 2-Methylthio-naphthacene-5,12-dione

3.62 mmol of 2-fluoro-naphthacene-5,12-dione (prepared according to U.S.Pat. No. 4,522,754), 3.98 mmol of NaSCH₃, 10.86 mmol of potassiumcarbonate and 10 ml of DMSO are stirred at 25° C. for 3 minutes. Themixture is poured onto water. The crystals are filtered off anddissolved in tetrahydrofuran/toluene and the solution is dried oversodium sulfate and evaporated. The residue is recrystallized fromTHF/toluene/pentane. Yield 1 g (83%); melting point 195°-196° C.

b) Methyl-(2-naphthacene-5,12-dionyl) sulfoxide

10 g (32.86 mmol) of 2-methylthio-naphthacene-5,12-dione, 3.72 g (32.86mmol) of 30% H₂ O₂ and 110 ml of glacial acetic acid are stirred at 80°C. for 4 hours. The mixture is cooled and taken up in methylenechloride/water. The organic phase is separated off, washed three timeswith water and three times with NaHCO₃ solution, dried over sodiumsulfate and concentrated. 7.72 g (73%) of pure sulfoxide are obtained bychromatography (mobile phase: 15% acetone, 85% CH₂ Cl₂) over silica gel,melting point 260°-263° C.

Examples 36-40

Dimethyl (2-naphthacene-5,12-dionyl)-malonate

50 g (181 mmol) of 2-fluoro-naphthacene-5,2-dione, 71.74 g (543 mmol) ofdimethyl malonate, 75.04 g (543 mmol) of potassium carbonate and 500 mlof DMSO are stirred at a bath temperature of 100° C. for 2 hours. Aftercooling, the mixture is poured onto dilute hydrochloric acid. Theprecipitate is filtered off, washed with water and methanol and thenrecrystallized from toluene. Yield 63.97 g (91%); melting point211°-215° C.

The procedure in Examples 37 to 40 is analogous (see Table 4):

                  TABLE 4                                                         ______________________________________                                         ##STR26##                                                                                        Reaction                                                                              Bath                                                                  time    temp. Yield m.p.                                  Example                                                                              R            (hours) (°C.)                                                                        (%)   (°C.)                          ______________________________________                                        37                                                                                    ##STR27##    2      100   79    134-140                               38                                                                                    ##STR28##   24      60    75    210-215                               39                                                                                    ##STR29##    3      60    73    212-217                               40                                                                                    ##STR30##   42      60    44    220-223                               ______________________________________                                    

Example 41

(2-Naphthacene-5,12-dionyl)-acetic acid

8 g (20.6 mmol) of dimethyl (2-naphthacene-5,12-dionyl)-malonate(Example 36), 60 ml of glacial acetic acid and 60 ml of concentrated HClsolution are stirred under reflux for 4.5 hours. The mixture is pouredonto ice/water. The crystals are filtered off, washed with diethyl etherand recrystallized from THF/pentane. Yield 4.88 g (75%); meltingpoint >220° C.

Example 42

1-Nitro-naphthacene-5,12-dione

30 g (147.7 mmol) of 5-nitronaphtho-1,4-quinone, 58.02 g (about 220mmol) of 1,2-dibromobenzocyclobutene (contaminated with a little1-iodo-2-bromobenzocyclobutene) and 300 ml of toluene are stirred underreflux for 2 days, the hydrobromic acid formed being distilled offtogether with a little toluene and the toluene lost in this way beingreplaced by fresh toluene. The mixture is cooled to 25° C. and theprecipitate is filtered off, washed with toluene and dried in vacuo at140° C. Yield: 43.46 g (97%); melting point >250° C. The product can berecrystallized from -butyrolactone; yield; 77%.

Examples 43-51

1-Phenoxy-naphthacene-5,12-dione

3 g (9.9 mmol) of 1-nitronaphthacene-5,12-dione (Example 42), 2.73 g(19.8 mmol) of potassium carbonate, 1.39 g (14.8 mmol) of phenol and 30ml of DMSO are stirred at a bath temperature of 100° C. for 6 hours.After cooling, the mixture is partitioned between methylenechloride/dilute hydrochloric acid. The organic phase is separated off,washed with water, dried over sodium sulfate and evaporated. The productis obtained in a pure form by chromatography on silica gel (mobilephase: methylene chloride); yield 2.52 g (73%); melting point 195°-200°C.

The procedure in Examples 44-51 is analogous (see Table 5):

                                      TABLE 5                                     __________________________________________________________________________     ##STR31##                                                                    Example                                                                            R              Reaction time (hours)                                                                    Bath temp. (°C.)                                                                Yield (%)                                                                           m.p. (°C.)               __________________________________________________________________________    44   OCH.sub.3      23         100      68    260-262                         45   SCH.sub.3 *.sup.)                                                                             1/3       25       56    260-265                         46   SCH.sub.2 CH.sub.3                                                                            1         25       48    200-205                         47   SCH.sub.2CH.sub.2OH                                                                          1,5        25       30    250-255                         48                                                                                  ##STR32##     1,5        25       54    255-258                         49                                                                                  ##STR33##     24         80       39    210-215                         50                                                                                  ##STR34##     20         80       65    205-206                         51                                                                                  ##STR35##     20         80       28    205-206                         __________________________________________________________________________     *.sup.) NaSCH.sub.3 is used here instead of the mercaptan.               

Example 52

2-Fluoro-3-methoxy-naphthacene-5,12-dione

1 g (3.4 mmol) of 2,3-difluoronaphthacene-5,12-dione, 0.94 g (6.8 mmol)of potassium carbonate, 3.24 g of methanol and 20 ml of tetrahydrofuran(THF) are stirred at 25° C. for 18 hours and under reflux for 3 days.The mixture is cooled and dilute hydrochloric acid is added. The productis filtered off, washed with water, dried and chromatographed withmethylene chloride on silica gel. Sublimation under 1.3×10⁻¹bar/180°-310° C. gives 0.26 g (25%) of pure product, melting point >250°C.

Example 53

2,3-Dimethoxy-naphthacene-5,12-dione

1 g (3.4 mmol) of 2,3-difluoro-naphthacene-5,12-dione, 0.94 g (6.8 mmol)of K₂ CO₃, 2.18 g of methanol and 20 ml of DMSO are stirred at 110° C.for 22 hours. The mixture is poured onto dilute hydrochloric acid. Theproduct is filtered off, washed four times with water, dried andrecrystallized from CH₂ Cl₂ /pentane; yield 0.72 g (67%); meltingpoint >250° C.

Example 54

2-Fluoro-3-(N-morpholino-)-naphthacene-5,12-dione

1 g (3.4 mmol) of 2,3-difluoro-naphthacene-5,12-dione, 0.94 g (6.8 mmol)of potassium carbonate, 1.48 g (17 mmol) of morpholine and 20 ml of THFare stirred under reflux for 23 hours. The mixture is poured onto water.The product is filtered off, washed with water, dried and recrystallizedfrom dioxane; yield 0.78 g (64%); melting point >240° C.

Example 55

Dimethyl 2-(3-fluoro-naphthacene-5,12-dionyl)-malonate

1 g (3.4 mmol) of 2,3-difluoro-naphthacene-5,12-dione, 0.94 g (6.8 mmol)of potassium carbonate, 0.89 g (6.8 mmol) of dimethyl malonate and 20 mlof DMSO are stirred at 50° C. for 22 hours. The mixture is poured ontodilute hydrochloric acid and extracted with THF/toluene. The organicphase is washed with water, dried over sodium sulfate and evaporated.The product is purified by chromatography over silica gel (mobile phase:1% acetone/99% CH₂ Cl₂); yield 1.25 g (91%); melting point 225°-230° C.

Example 56

2-Cyano-naphthacene-5,12-dione

10 g (33.2 mmol) of naphthacene-5,12-dione-2-carboxamide, 10.18 g (66.4mmol) of POCl₃ and 200 ml of DMF are stirred at 10° C. and then at 25°C. for 2 hours. The mixture is poured onto ice-water. The precipitate isfiltered off, washed three times with water and dried. Whenrecrystallized from o-dichlorobenzene, 7.35 g (78%) of crude product areobtained.

IR spectrum (KBr): 1678 cm⁻¹ : Quinone; 2240 cm⁻¹ : CN Mass spectrum:M/e=283 (M⁺) (base peak); 255; 227; 226; 100.

Example 57

2-(Trifluoromethyl-)-naphthacene-5,12-dione

5.65 g (25 mmol) of 6-(trifluoromethyl)-1,4-naphthoquinone, 9.82 g(about 37 mmol) of 1,2-dibromobenzocyclobutene (contaminated with alittle 2-bromo-1-iodobenocyclobutene) and 100 ml of xylene are keptunder reflux for 16 hours, using a water separator. The mixture iscooled and the precipitate is filtered off and washed with xylene. Yield5.82 g (71%); melting point 253°-254° C. The procedure in Examples 58 to61 is analogous.

Example 58

2,3-bis-(Trifluoromethyl)-naphthacene-5,12-dione; yield 59%; meltingpoint >280° C.

Example 59

Methyl 1-(trifluoromethyl)-naphthacene-5,12-dione-3-carboxylate; yield60%. melting point 234°-235° C.

Example 60

Methyl 2-ethoxy-naphthacene-5,12-dione-3-carboxylate; yield 30%; meltingpoint 192°-194° C.

Example 61

Diethyl 2-ethoxy-naphthacene-5,12-dione-3-dicarboxylate; yield 41%;melting point 163°-164° C.

Starting substances:

The substituted naphthoquinones of Examples 57 to 60 are obtained by aDiels-Alder reaction of corresponding α-pyrones with p-benzoquinone, thetrifluoromethyl derivatives being prepared by fluorination of thecarboxylic acid ethyl ester with HF/SF₄. The naphthoquinone of Example60 is obtained by a Diels-Alder reaction of1-ethoxy-2,4-dicarbethoxy-1,4-butadiene with p-benzoquinone.

Examples 62-64

A mixture of 1 mol of the appropriately substituted dibromo- orbromoiodo-benzocyclobutene¹, 1.5 mol of naphthoquinone and 7 liters ofsolvent is heated under reflux for 4-16 hours. After cooling, thenaphthacenequinone which has precipitated is filtered off and purifiedby crystallization or sublimation under a high vacuum (see Table 6)

                                      TABLE 6                                     __________________________________________________________________________    Example No.                                                                           R      Solvent   Reaction time (hours)                                                                     Yield (%)                                                                            m.p. (°C.)                                                                   Mass spectrum (M.sup.+                                                        /%)                         __________________________________________________________________________    62.sup.1                                                                              Br     Xylene    16          50     >270  336/90                      63.sup.1                                                                              COOCH.sub.3                                                                          Dichlorobenzene                                                                         16          10      268  316/100                     64.sup.2                                                                              NO.sub.2                                                                             Dichlorobenzene                                                                          4          22     >270  303/100                     __________________________________________________________________________     .sup.1) recrystallized from toluene                                           .sup.2) sublimed at 200° C.                                            .sup.1 prepared by reaction of appropriately substituted                      odihalogeno-methyl-benzenes with NaI in acetonitrile at 80° C.    

Examples 65-95

A mixture of 0.1 mol of appropriately substitutedbis-dibromomethylbenzene, 0.12-0.2 mol of unsubstituted or substitutednaphthoquinone, 0.6 mol of sodium iodide and 1000 ml of acetone oracetonitrile is boiled under reflux for 2-6 hours, while stirring andunder an N₂ atmosphere. After cooling, the precipitate which hasseparated out is filtered off and digested with water. The substitutednaphthacenedione obtained in this manner is either recrystallized orsublimed under a high vacuum for further purification (cf. Tables 7,8and 9).

                                      TABLE 7                                     __________________________________________________________________________     ##STR36##                                                                                      Reaction                                                    Example No.                                                                          R   Solvent                                                                              time (hours)                                                                         Recrystallization/sublimation                                                               Yield (%)                                                                           m.p. (°C.)                                                                   Mass spectrum (M.sup.+                                                        /%)                        __________________________________________________________________________     .sup. 65.sup.a)                                                                     Me.sub.3 Si                                                                       Acetonitrile                                                                         5      Sublim. 150° C.                                                                      79    168-170                          66     F   Acetonitrile                                                                         2      Sublim. 200° C.                                                                      68    >270  276/100                    __________________________________________________________________________     .sup.a) The filtrate is evaporated to dryness, the residue is dissolved i     CH.sub.2 Cl.sub.2 and the solution is washed with NAHSO.sub.3 and dried.      The residue is then subjected to steam distillation and the nonvolatile       portions are extracted with ether, dried and then sublimed.              

                                      TABLE 8                                     __________________________________________________________________________     ##STR37##                                                                                                      Reaction                Mass                                                  time  Recrystallization/                                                                     Yield                                                                             m.p. spectrum            Example No.                                                                          R.sup.6                                                                            R.sup.7                                                                            R.sup.2                                                                            R.sup.3                                                                            Solvent                                                                              (hours)                                                                             sublimation                                                                            (%) (°C.)                                                                       (M.sup.+            __________________________________________________________________________                                                              /%)                 67     OCH.sub.3                                                                          H    CF.sub.3                                                                           CF.sub.3                                                                           Acetonitrile                                                                         5     Sublim. 200° C.                                                                 33  >280 424/100             68     OCH.sub.3                                                                          H    COOEt                                                                              COOEt                                                                              Acetonitrile                                                                         5     Sublim. 180° C.                                                                 40  214-216                                                                            432/90              69     OCH.sub.3                                                                          H    CH.sub.3                                                                           CH.sub.3                                                                           Acetone                                                                              5     Sublim. 180° C.                                                                 13  268-270                                                                            316/100             70     Me.sub.3 Si                                                                        Me.sub.3 Si                                                                        H    H    Acetonitrile                                                                         3     Sublim. 180° C.                                                                 70  196-197                                                                            405/55               .sup. 71.sup.b)                                                                     Me.sub.3 Si                                                                        Me.sub.3 Si                                                                        COOEt                                                                              COOEt                                                                              Acetonitrile                                                                         3     Isopropyl ether                                                                        64  138-139                                                                            546/80              72     CN   CN   COOEt                                                                              COOEt                                                                              CH.sub.3 CN                                                                          5     Sublim.  44  >270 452/10              73     CN   CN   H    H    CH.sub.3 CN                                                                          5     Sublim.  71  >270 308/100             74     Br   Br   H    H    CH.sub.3 CN                                                                          4     Sublim.  60  >250 416/100             75     Br   Br   COOEt                                                                              COOEt                                                                              CH.sub.3 CN                                                                          4     Sublim.  53  >250 560/64              76     Br   Br   CF.sub.3                                                                           CF.sub.3                                                                           CH.sub.3 CN                                                                          4     Sublim.  58  >250 552/100             77     CF.sub.3                                                                           CF.sub.3                                                                           Cl   COOEt                                                                              CH.sub.3 CN                                                                          6     Sublim.  68  >270 500/60              78     CF.sub.3                                                                           CF.sub.3                                                                           CF.sub.3                                                                           CF.sub.3                                                                           CH.sub.3 CN                                                                          8     Sublim.  70  >280 530/100             79     CF.sub.3                                                                           H    COOEt                                                                              COOEt                                                                              Acetone                                                                              5     Sublim.  60  216-217                                                                            470/40              80     CF.sub.3                                                                           H    CF.sub.3                                                                           CF.sub.3                                                                           Acetone                                                                              5     Sublim.  55  261-262                                                                            462/100             81     Cl   Cl   H    H    CH.sub.3 CN                                                                          5     Sublim.  54  >250 326/100             82     Cl   Cl   CF.sub.3                                                                           CF.sub.3                                                                           CH.sub.3 CN                                                                          5     Sublim.  41  >250 462/100             83     Cl   Cl   COOEt                                                                              COOEt                                                                              CH.sub.3 CN                                                                          5     Sublim.  68  >250 470/48              84     COOMe                                                                              COOMe                                                                              H    H    CH.sub.3 CN                                                                          4     Sublim.  67  >250 374/48              85     COOMe                                                                              COOMe                                                                              COOEt                                                                              COOEt                                                                              CH.sub.3 CN                                                                          4     Sublim.  70  238-239                                                                            518/88              86     COOMe                                                                              COOMe                                                                              CF.sub.3                                                                           CF.sub.3                                                                           CH.sub.3 CN                                                                          5     Sublim.  72  >250 510/40              87     Me.sub.3 Si                                                                        Me.sub.3 Si                                                                        CF.sub.3                                                                           CF.sub.3                                                                           CH.sub.3 CN                                                                          5     Isopropyl ether                                                                        30  143-145                                                                            538/60              __________________________________________________________________________     .sup.b) The filtrate is evaporated to dryness, the residue is dissolved i     ether and the solution is washed with NaHSO.sub.3 and dried. The ether        residue is filtered over a silica gel column with CH.sub.2 Cl.sub.2.     

                                      TABLE 9                                     __________________________________________________________________________     ##STR38##                                                                                                         Reaction            Mass                 Example                              time  sublimation                                                                         Yield                                                                             m.p.                                                                              spectrum             No.  R.sup.1                                                                            R.sup.2                                                                             R.sup.3                                                                             R.sup.4                                                                          R.sup.5                                                                           Solvent (hours)                                                                             (°C.)                                                                        (%) (°C.)                                                                      (M.sup.+             __________________________________________________________________________                                                             /%)                  88   H    COOCH.sub.3                                                                         H     H  OCH.sub.3                                                                         Acetone 5     180   50  246-248                                                                           346/95               89   NO.sub.2                                                                           H     H     H  OCH.sub.3                                                                         Acetone 5     180   28  >280                                                                              333/95               90   CF.sub.3                                                                           H     COOCH.sub.3                                                                         H  OCH.sub.3                                                                         Acetone 5     200   80  235-240                                                                           414/100              91   COOEt                                                                              OEt   COOEt H  OCH.sub.3                                                                         Acetone 5     220   16  230-232                                                                           476/60               92   H    COOCH.sub.3                                                                         H     CF.sub.3                                                                         CF.sub.3                                                                          CH.sub.3 CN                                                                           6     240   50  >280                                                                              452/100              93   H    Cl    COOEt H  CF.sub.3                                                                          CH.sub.3 CN                                                                           6     230   60  >280                                                                              432/70               .sup.  94.sup.1)                                                                   H    F     H     H  F   Fluorobenzene                                                                         4     225   47  278-280                                                                           294/100              95   H    Cl    H     H  F   CH.sub.3 CN                                                                           6     270   26  >280                                                                              310/100              __________________________________________________________________________     These antracenediones are in the form of an approx. 1:1 mixture of the tw     possible isomers (OCH.sub.3 bonded in the 8 or 9position).                    .sup.1) Catalyst: AlCl.sub.3.                                            

B) USE EXAMPLES Example 96

Photocuring of an acrylate mixture for the preparation of a reliefimage.

A photocurable composition is prepared by mixing the followingcomponents:

    ______________________________________                                                               Solids content                                         ______________________________________                                        150.30 g                                                                              of Scripset 540.sup.1) (30% solution                                                               45.1 g                                                   in acetone)                                                            48.30 g                                                                              of trimethylolpropane triacrylate                                                                  48.3 g                                            6.60 g of polyethylene glycol diacrylate                                                                   6.6 g                                            0.08 g of crystal violet                                                     205.28 g                     100.0 g                                          ______________________________________                                         .sup.1) Polystyrene/maleic acid halfester copolymer (Monsanto)           

Portions of this composition are mixed with 0.2% (based on thecomposition) of the photoinitiators listed in the following table. Allthe operations are performed under red light or yellow light.

The samples to which initiator has been added are applied with a spiraldoctor of 150 μm to 200 μm aluminium foil (10×15 cm). The solvent isremoved by heating at 60° C. in a circulating air oven for 15 minutes. Adry layer thickness of about 35 μm results. A 76 μm thick polyester filmis placed on the layer, and a standardized test negative with 21 stepsof different optical density (Stouffer wedge) is placed on this. Asecond polyester film is placed on top and the laminate thus obtained isfixed onto a metal plate by means of vacuum. The sample is then exposedto a 5 KW metal halide lamp (type MO 23) at a distance of 30 cm, and inparticular for 20 seconds in a first test series and for 40 seconds in asecond test series. After the exposure, the films and mask are removedand the exposed layer is developed in a ultrasonic bath with developer Afor 2 minutes and then dried at 60° C. in a circulating air oven for 15minutes. The sensitivity of the initiator system used is characterizedby stating the last wedge step imaged without tackiness. The higher thenumber of steps, the more sensitive the system. An increase by two stepshere means approximately a doubling of the rate of curing. The resultsare shown in Table 10. Developer A contains 15 g of sodiummetasilicate.9 H₂ O; 0.16 g of KOH; 3 g of polyethylene glycol 6000; 0.5g of levulinic acid and 1000 g of deionized water.

                  TABLE 10                                                        ______________________________________                                        Photoinitiator                                                                Naphthacenedione of                                                                        No. of steps imaged                                              example      after 20 sec.                                                                             after 40 sec. exposure                               ______________________________________                                         2           3           5                                                     7           2           4                                                    35           3           5                                                    37           2           4                                                    44           5           7                                                    88           1           2                                                    A.sup.1      3           5                                                    B.sup.2      2           4                                                    ______________________________________                                         .sup.1) Methyl 2anthracene-5,12-dionecarboxylate                              .sup.2) 6-Methoxyanthracene-5,12-dione                                   

Example 97

A solution having the composition:

    ______________________________________                                        Ethylcellosolve       71.00 g                                                 Scripset 550*.sup.)   14.00 g                                                 Trimethylolpropane triacrylate                                                                      15.00 g                                                 Polyethylene glycol 200 diacrylate                                                                  2.00 g                                                  ______________________________________                                         *.sup.) Styrene/maleic acid monoester copolymer (M.sub.w = 10000, acid no     190), manufacturer Monsanto   is divided into equal portions of 10 grams      each. In each case 0.05 g of naphthacenedione and 0.5 g of glycerol are     dissolved in this solution under red light.

Coatings are applied with a wire doctor in a wet film thickness of 12micrometers onto transparent polyester film. The wet films are dried at80° C. in a circulating air oven for 30 minutes.

An oxygen barrier layer 0.5 micrometers thick is applied by dipping intoa solution of

    ______________________________________                                        Mowiol 4-88 (polyvinyl alcohol)                                                                    30.00 g                                                  Brij 35 (10% in water)**.sup.)                                                                     15.00 g                                                  Deionized water      250.00 g                                                 ______________________________________                                         **.sup.) Polyoxyethylene lauryl ether (wetting agent, manufacturer Atlas      Powder)                                                                  

and subsequent drying at 80° C. in a circulating air oven.

The dry film is exposed with a 5000 W mercury lamp (MO 33, Staub, NeuIsenburg) through a step wedge with increments of 0.15 (log O.D.) andthen developed in a solution having the composition

    ______________________________________                                        Sodium metasilicate nonahydrate                                                                    15.00 g                                                  Strontium hydroxide octahydrate                                                                    0.30 g                                                   Polyglycol 6000      3.00 g                                                   Levulinic acid       0.50 g                                                   Deionized water      1000.00 g                                                ______________________________________                                    

to give a relief image. The light intensity is measured with aPowermeter from Oriel with a 365 nm sensor. Table 11 shows the exposureenergy required to achieve step 7 of the step wedge.

                  TABLE 11                                                        ______________________________________                                        Naphthacenedione                                                                           UV spectrum     WP.sub.7                                         of Example   (extinction at λ.sub.max)                                                              mJ/cm.sup.-2)                                    ______________________________________                                        37           ε = 6100, λ.sub.max : 398 nm                                                   660                                                           shoulder at 414 nm                                               ______________________________________                                    

Example 98

Photometallization

A copolymer of 65 mol % of hydroxypropyl methacrylate and 35 mol % ofmethyl methacrylate having a molecular weight of 120000 Daltons(measured by light scattering in dioxane at 25° C.) is dissolved in DMF,and 5 mol % of anthracenedione according to Example 37 (based on thepolymer hydroxyl groups) is added. Films are produced by doctor-coatingthe solution onto a polyester carrier and subsequent drying at 80° C. ina circulating air oven for 2 hours. The films are exposed on athermostatically controllable vacuum heating bench at 50° C. under anegative using a Hg high pressure lamp of 40 mW/cm⁻² intensity. A darknegative image of the master is obtained and is reinforced in adeposition bath having the composition

    ______________________________________                                        CuSO.sub.4 × 5H.sub.2 O                                                                   0.0665      mol/l                                           HCOH              0.0467      mol/l                                           Quadrol           0.0599      mol/l                                           NaOH              pH          12.6                                            NaCN              25          mg/l                                            2-Mercaptobenzothiazole                                                                         10          mg/l                                            ______________________________________                                    

at 45° C. to give a copper image.

Example 99

Sensitization of 2+2 cycloaddition 5% (w/w) of2-methoxy-anthracene-5,12-dione is dissolved in a 20% (w/w) solution ofa copolymer having a molecular weight of 140000 Daltons (measured bylight scattering in dioxane at 25° C.) and consisting of 20 mol % ofethyl acrylate and 80 mol % ofN-(5-methyl-3-oxa-4-oxohexen-5-yl)-dimethylmaleimide (prepared by theprocess in Angew. Makromol, Chem. 115 (1983) 163 et seq.). The solutionis doctor-coated with a wire doctor as a film in a wet film thickness of24 μm onto a copper-coated glass fibre-epoxide laminate and dried at 80°C. for 1 hour. The dry film is exposed with a 5000 W mercury lamp (MO33, Staub) through a step wedge with increments of 0.15 (log O.D.) andthen developed in 1,1,1-trichloroethane to give a relief image. Theexposure energy required to achieve step 7 of the step wedge is 231mJ×cm⁻².

What is claimed is:
 1. A compound of the formula ##STR39## wherein (a)R₅, R₆, R₇ and R₈ are H, and(a1) R₁ and R₄ are independently of eachother selected from the group consisting of H, --NO₂, --CF₃, --CN,COOR₉, --CONR₉ R₁₀, --COCl, --Si(C₁ -C₄ alkyl)₃, --S(C_(m) H_(2m)--O--)_(n) R₁₁, --O(C_(m) H_(2m) --O--)_(n) R₁₁, substituted orunsubstituted C₁ -C₂₀ alkyl-(X₁ --)_(p), C₂ -C₁₈ alkenyl-(X₁ --)_(p), C₂-C₁₈ alkynyl-(X₁ --)_(p), C₃ -C₈ cycloalkyl-(X₁ --)_(p), (C₁ -C₁₂alkyl)C₃ -C₈ cycloalkyl-(X₁ --)_(p), C₃ -C₈ cycloalkylC_(r) H_(2r) -(X₁--)_(p), (C₁ -C₁₂ alkyl)C₃ -C₈ cycloalkyl C_(r) H_(2r) --(X₁ --)_(p),phenyl-(X₁ --)_(p),(C₁ -C₁₂ alkyl)phenyl-(X₁ --)_(p), phenylC_(r) H_(2r)--(X--).sub. p, (C₁ -C₁₂ alkyl)phenylC_(r) H_(2r) --(X--)_(p),substituted C₁ -C₂₀ alkylthio and phenyloxy, (C₁ -C₁₂ alkyl)phenyloxy orC₁ -C₂₀ alkoxy which is substituted by halogen, --CN, --NR₉ R₁₀, --SR₉,--OR₉ or --COOR₉, wherein R₁ is additionally selected from the groupconsisting of unsubstituted C₁ -C₂₀ alkylthio, phenyloxy, phenylthio, C₁-C₁₂ alkylphenyloxy and substituted C₁ -C₁₂ alkylphenylthio; and (a2) R₂and R₃ each are independently selected from the group consisting of H,substituted C₅ -C₂₀ -alkyl, unsubstituted C₈ -C₁₈ alkoxy, substituted C₃-C₂₀ alkoxy, unsubstituted or substituted C₁ -C₂₀ alkyl-(X₁ --)_(p) --,phenyl-(X)_(p) --, (C₁ -C₁₂ alkyl)phenyl-(X--)_(p), phenylC_(r) H_(2r)--(X--)_(p), (C₁ -C₁₂ alkyl)phenylC_(r) H_(2r) --(X--)_(p), C₂ -C₁₈alkenyl-(X--)_(p), C₂ -C₁₈ alkynyl-(X--)_(p), C₃ -C₈cycloalkyl-(X--)_(p), (C₁ -C₁₂ alkyl)C₃ -C₈ cycloalkyl-(X--)_(p), C₃ -C₈cycloalkylC_(r) H_(2r) --(X--)_(p) --, and (C₁ -C₁₂ alkyl)C₃ -C₈cycloalkylC_(r) H_(2r) --(X--)_(p), or (a3) one of R₂ and R₃ or both ofR₂ and R₃ are selected from the group consisting of C₁ -C₄ alkyl whichis substituted by halogen, --CN, --NR₉ R₁₀, --SR₉, --OR₉ or --COOR₉ andC₁ -C₂ -alkoxy which is substituted by halogen, --CN, --NR₉ R₁₀, --SR₉,--OR₉ --COOR₉, or (a4) one of R₂ and R₃ or both of R₂ and R₃ areselected from the group consisting of --SH, --NO₂, --CF₃, --NR₉ R₁₀,--O(C_(m) H_(2m) --O--)_(n) R₁₁, and --Si(C₁ -C₄ alkyl)₃, or (a5) one ofR₂ and R₃ is halogen, --COOR₉ --NR₉ R₁₀ or COCl and the other of R₂ andR₃ is selected from the group consisting of --NO₂, --CF₃, --CN, --NR₉R₁₀, --SH, --O(C_(m) H_(2m) --O--)_(n) R₁₁, --Si(C₁ -C₄ alkyl)₃, C₁ -C₂₀alkyl-(X--)_(p), C₂ -C₁₈ alkenyl-(X--)_(p), C₂ -C₁₈ alkynyl-(X--)_(p),C₃ -C₈ -cycloalkyl-(X--)_(p), (C₁ -C₁₂ alkyl)C₃ -C₈cycloalkyl-(X--)_(p), C₃ -C₈ cycloalkylC_(r) H_(2r) --(X--)_(p), (C₁-C₁₂ alkyl)C₃ -C₈ cycloalkylC_(r) H_(2r) --(X--)_(p), phenyl-(X--)_(p),(C₁ -C₁₂ alkyl)phenyl-(X--)_(p), phenylC_(r) H_(2r) --(X--)_(p), and (C₁-C₁₂ alkyl)phenylC_(r) H_(2r) --(X-- )_(p), which are unsubstituted orsubstituted, or the other of R₂ and R₃ is H, if at least one or R₁ andR₄ is not hydrogen, or (a6) R₂ and R₃ together are --CO--O--CO-- or--CO--NR₉ --CO-- and at least one of R₁ and R₄ is not hydrogen; andwherein X₁ is --SO-- or --SO₂ -- and X is --O--, --SO-- or --SO₂ --; R₉and R₁₀ independently of one another are C₁ -C₁₂ alkyl, phenyl or(--C_(m) H_(2m) --O--)_(q) R₁₁, or R₉ and R₁₀ together aretetramethylene, pentamethylene, 3-oxapentylene or --CH₂ CH₂ NR₉ CH₂ CH₂--, R₁₁ is H or C₁ -C₁₂ alkyl, m is a number from 2 to 4, n is a numberfrom 2 to 20, p is 1, q is a number from 1 to 20 and r is 1 or 2; andwherein substituted R₁, R₂, R₃ and R₄ groups are substituted by halogen,--CN, furfuryl, --NR₉ R₁₀, --OR₉, --SR₉ or COOR₉ unless otherwisespecified; with the provisos that at least one of R₁, R₂, R₃ or R₄ isother than hydrogen.
 2. A compound of claim 1 whereinR₁ is --NO₂, --CF₃or --COO(C₁ -C₄ alkyl); R₄ is H; and R₂ and R₃ are independently of oneanother C₃ to C₁₈ alkoxy, C₃ -C₁₂ hydroxyalkyl or C₃ -C₆ dihydroxyalkyl;C₃ -C₁₂ alkenoxy or C₃ -C₆ alkynoxy, in which the --O-- atom is notbonded to the alkene or alkyne group, or --O--(CH₂ CH₂ --O--)_(n) R¹¹where n is 2 to 12 and R¹¹ is H or C₁ -C₆ alkyl; phenyloxy which isunsubstituted or substituted by --F, --Cl, C₁ -C₄ alkyl, C₁ -C₄ alkoxyor C₁ -C₄ alkylthio; --NR⁹ R¹⁰, where R⁹ and R¹⁰ are C₁ -C₆ alkyl, ortogether are pentamethylene or 3-oxapentylene; C₁ -C₆ -alkyl-SO--, C₁-C₆ alkyl-SO₂ --, phenyl-SO-- or phenyl-SO₂ --; C₁ -C₄ alkyl or benzylwhich are substituted by --CN or COO(C₁ -C.sub. 6 alkyl); or CN, --CF₃,--F, --Cl or --Br.
 3. A compound of claim 1 wherein(b1) R₁ and R₄ areindependently of each other selected from the group consisting of H,--NO₂, --CF₃, --CN, COOR₉, --CONR₉ R₁₀, --COCl, --Si(C₁ -C₄ alkyl)₃,--S(C_(m) H_(2m) --O--)_(n) R₁₁, --O(C_(m) H_(2m) --O--)_(n) R₁₁,substituted or unsubstituted C₁ -C₂₀ alkyl-(X₁ --)_(p), C₂ -C₁₈alkenyl-(X₁ --)_(p), C₂ -C₁₈ alkynyl-(X₁ --)_(p), C₃ -C₈ cycloalkyl-(X₁--)_(p), (C₁ -C₁₂ alkyl)C₃ -C₈ cycloalkyl-(X₁ --)_(p), C₃ -C₈cycloalkylC_(r) H_(2r) --(X₁ --)_(p), (C₁ -C₁₂ alkyl)C₃ -C₈ cycloalkylC_(r) H_(2r) --(X₁ --)_(p), phenyl-(X₁ --)_(p), (C₁ -C₁₂alkyl)phenyl-(X₁ --)_(p), phenylC_(r) H_(2r) -- (X--)_(p), (C₁ -C₁₂alkyl)phenylC_(r) H_(2r) --(X--)_(p), substituted C₁ -C₂₀ alkylthio andphenyloxy or (C₁ -C₁₂ alkyl)phenyloxy which is substituted by halogen,--CN, --NR₉ R₁₀, --SR₉, --OR₉ or --COOR₉, wherein R₁ is not --COOH ifR₂, R₃ and R₄ are H; and wherein R₁ is additionally selected from thegroup consisting of unsubstituted C₁ -C₂₀ alkylthio, phenyloxy,phenylthio, C₁ -C₁₂ alkylphenyloxy and substituted C₁ -C₁₂alkylphenylthio; and (b2) R₂ and R₃ each are independently selected fromthe group consisting of H, --SH, --NO₂, --CF₃, --NR₉ R₁₀, --O(C_(m)H_(2m) --O--)_(n) R₁₁, --Si(C₁ -C₄ alkyl)₃, unsubstituted or substitutedC₁ -C₂₀ alkyl-(X₁ --)_(p) --, phenyl-(X)_(p) --, (C₁ -C₁₂alkyl)phenyl-(X--)_(p), phenylC_(r) H_(2r) --(X--)_(p), (C₁ -C₁₂alkyl)phenylC_(r) H_(2r) --(X--)_(p), C₂ -C₁₈ alkenyl-(X--)_(p), C₂ -C₁₈alkynyl-(X--)_(p), C₃ -C₈ cycloalkyl-(X--)_(p), (C₁ -C₁₂ alkyl)C₃ -C₈cycloalkyl-(X--)_(p), C₃ -C₈ cycloalkylC_(r) H_(2r) --(X--)_(p) --, (C₁-C₁₂ alkyl)C₃ -C₈ cycloalkylC_(r) H_(2r) --(X--)_(p).
 4. A compound ofclaim 1 wherein(c1) R₁ and R₄ are independently of each other selectedfrom the group consisting of H, --NO₂, --CF₃, --CN, COOR₉, --CONR₉ R₁₀,--COCl, --Si(C₁ -C₄ alkyl)₃, --S(C_(m) H_(2m) --O--)_(n) R₁₁, --O(C_(m)H_(2m) --O--)_(n) R₁₁, substituted or unsubstituted C₁ -C₂₀ alkyl-(X₁--)_(p), C₂ -C₁₈ alkenyl-(X₁ --)_(p), C₂ -C₁₈ alkynyl-(X₁ --)_(p), C₃-C₈ cycloalkyl-(X₁ --)_(p), (C₁ -C₁₂ alkyl)C₃ -C₈ cycloalkyl-(X₁--)_(p), C₃ -C₈ cycloalkylC_(r) H_(2r) --(X₁ --)_(p), (C₁ -C₁₂ alkyl)C₃-C₈ cycloalkylC_(r) H_(2r) --(X₁ --)_(p), phenyl-(X₁ --)_(p), (C₁ -C₁₂alkyl)phenyl-(X₁ --)_(p), phenylC_(r) H_(2r) --(X-- )_(p), (C₁ -C₁₂alkyl)phenylC_(r) H_(2r) --(X--)_(p), substituted C₁ -C₂₀ alkylthio andphenyloxy or (C₁ -C₁₂ alkyl)phenyloxy which is substituted by halogen,--CN, --NR₉ R₁₀, --SR₉, --OR₉ or --COOR₉, wherein R₁ is not --COOH ifR₂, R₃ and R₄ are H; and wherein R₁ is additionally selected from thegroup consisting of unsubstituted C₁ -C₂₀ alkylthio, phenyloxy,phenylthio, C₁ -C₁₂ alkylphenyloxy and substituted C₁ -C₁₂alkylphenylthio; and (c5) one of R₂ and R₃ is halogen, --COOR₉ --NR₉ R₁₀or COCl and the other of R₂ and R₃ is selected from the group consistingof --NO₂, --CF₃, --CN, --NR₉ R₁₀, --SH, --O(C_(m) H_(2m) --O--)_(n) R₁₁,--Si(C₁ -C₄ alkyl)₃, C₁ -C₂₀ alkyl-(X--)_(p), C₂ -C₁₈ alkenyl-(X--)_(p),C₂ -C₁₈ alkynyl-(X--)_(p), C₃ -C₈ cycloalkyl-(X--)_(p), (C₁ -C₁₂alkyl)C₃ -C₈ cycloalkyl-(X--)_(p), C₃ -C₈ cycloalkylC_(r) H_(2r)--(X--)_(p), (C₁ -C₁₂ alkyl)C₃ -C₈ cycloalkylC_(r) H_(2r) --(X--)_(p),phenyl-(X--)_(p), (C₁ -C₁₂ alkyl)phenyl-(X--)_(p), phenylC_(r) H_(2r)--(X--)_(p), and (C₁ -C₁₂ alkyl)phenylC_(r) H_(2r) -- (X--)_(p), whichare unsubstituted or substituted, or the other of R₂ and R₃ is H, if atleast one or R₁ and R₄ is not hydrogen.
 5. A compound of claim 1 whereinR₂ and R₃ together are --CO--O--CO-- or --CO--NR₉ --CO-- and at leastone of R₁ and R₄ is not hydrogen.
 6. A compound according to claim 1, inwhich R⁴ is H and R¹ is --CF₃ or --COO(C₁ -C₄ -alkyl).
 7. A compoundaccording to claim 1, in which R¹ and R⁴ are H.
 8. A compound of claim 7selected from the group consisting of2-n-octyloxynaphthacene-5,12-dione.
 9. A compound according to claim 1,in which R⁵ to R⁸ are H and R¹ is unsubstituted C₁ -C₁₂ alkylthio, C₁-C₂ alkoxy, phenyloxy, (C₁ -C₆ alkyl)phenyloxy or (C₁ -C₆alkyl)phenylthio, or phenylthio or (C₁ -C₆ alkyl)phenylthio which issubstituted by --F, --Cl, --OH, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio.
 10. Acompound according to claim 1 in which one or both of R² and R³ is C₁-C₆ alkyl which is substituted by --CN or --COO(C₁ -C₁₂ alkyl), orbenzyl.